CeO2/TiO2 composite with kernel-shell structure was synthesized by a sol-gel process. The characterization results show that the composite is made up of anatase phase TiO2 and cubic system CeO2. The electrochemiluminescence (ECL) behavior of the CeO2/TiO2 composite was studied by a cyclic voltammetry in the presence of persulfate, and the effect factors on ECL emission were discussed. Based on a series of experiments, it is proposed that the strong dual ECL emission produced by the CeO2/TiO2 composite resulted from the benefit ECL effect of interface heterojunction in composite. (C) 2011 Elsevier Ltd. All rights reserved.